A Six-Vertex Theorem for Bounding Normal Planar Curves

We prove that the number of vertices of a smooth normal planarcurve is at least 6, if it bounds a surface other than the disk.     

Determination of thiamine HCl and pyridoxine HCl in pharmaceutical preparations using UV-visible spectrophotometry and genetic algorithm based multivariate calibration methods

Simultaneous determination of binary mixtures pyridoxine hydrochloride and thiamine hydrochloride in a vitamin combination using UV-visible spectrophotometry and classical least squares (CLS) and three newly developed genetic algorithm (GA) based multivariate calibration methods was demonstrated. The three genetic multivariate calibration methods are Genetic Classical Least Squares (GCLS), Genetic Inverse Least Squares (GILS) and Genetic Regression (GR). The sample data set contains the UV-visible spectra of 30 synthetic mixtures (8 to 40 microg/ml) of these vitamins and 10 tablets containing 250 mg from each vitamin. The spectra cover the range from 200 to 330 nm in 0.1 nm intervals. Several calibration models were built with the four methods for the two components. Overall, the standard error of calibration (SEC) and the standard error of prediction (SEP) for the synthetic data were in the range of <0.01 and 0.43 microg/ml for all the four methods. The SEP values for the tablets were in the range of 2.91 and 11.51 mg/tablets. A comparison of genetic algorithm selected wavelengths for each component using GR method was also included.     

Synthesis of 5,6-O-Cyclohexylidene-1-amino-3-azahexane and Its Co(II), Ni(II), Cu(II) Complexes

5,6-O-Cyclohexylidene-1-amino-3-azahexane (L) is synthesized from 1-chloro-2,3-O-cyclohexylidenepropane, which is prepared by the reaction between epichlorohydrin and cyclohexanone. In this reaction, BF₃ · OEt₂ is used as a catalyst. Complexes of Co(II), Ni(II) and Cu(II) acetates with this ligand are prepared. The structures of the ligand and its complexes are proposed based on elemental analysis, IR and UV-VIS spectroscopy, magnetic susceptibility, conductometry, and ¹H and ¹³C NMR spectroscopy.     

Effect of electrolytes on the surface behavior of rhamnolipids R1 and R2

The surface behavior of solutions of the rhamnolipids, R1 and R2, were investigated in the absence and presence of an electrolyte (NaCl) through surface tension measurements and optical microscopy at pH 6.8. The NaCl concentrations studied are 0.05, 0.5 and 1 M. Electrolytes directly affect the carboxylate groups of the rhamnolipids. The solution/air interface has a net negative charge due to the dissociated carboxylate ions at pH 6.8 with strong repulsive electrostatic forces between the rhamnolipid molecules. This negative charge is shielded by the Na⁺ ions in the electrical double layer in the presence of NaCl, causing the formation of a close-packed monolayer, and a decrease in CMC, and surface tension values. The maximum compaction is observed at 0.5 M NaCl concentrations for R1 and R2 monolayers, with the R1 monolayer more compact than R2. The larger spaces left below the hydrophobic tails of R1 with respect to that of R2, due to the missing second rhamnosyl groups are thought to be responsible for the higher compaction. The rigidity of both R1 and R2 monolayers increases with the electrolyte concentration. The rigidity of the R1 monolayer is greater than that of R2 at all NaCl concentrations due to the lower hydrophilic character of R1. The variation of CMC values as a function of NaCl concentration obtained from the surface tension measurements and critical packing parameter (CPP) calculations show that spherical micelles, bilayer and rod like micelles are formed in the rhamnolipid solutions as a function of the NaCl concentration. The results of optical microscopy supported these aggregation states indicating lamellar nematic liquid crystal, cubic lamellar and hexagonal liquid crystal phases in R1 and R2 solutions depending on the NaCl concentration.     

Synthesis and determination of pKa values of some new 3,4-disubstituted-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives in non-aqueous solvents

3-Alkyl(Aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) reacted with 2-furoyl chloride and thiophene-2-carbonyl chloride to afford the corresponding 3- alkyl(aryl)-4-(2-furoylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (3) and 3-alkyl(aryl)- 4-(2-thienylcarbonylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (4), respectively. The new compounds synthesized were characterized by using IR, 1H-NMR, 13C-NMR and UV spectral data together with elemental analysis. In addition, to investigate the effects of solvents and molecular structure upon acidity, compounds 3 and 4 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents (isopropyl alcohol, tert-butyl alcohol, N,N-dimethylformamide and acetonitrile). The half-neutralization potential values and the corresponding pKa values were determined for all cases.     

Eta6-mesityl,eta1-imidazolinylidene-carbene-ruthenium(II) complexes: catalytic activity of their allenylidene derivatives in alkene metathesis and cycloisomerisation reactions

The reaction of electron-rich carbene-precursor olefins containing two imidazolinylidene moieties [(2,4,6-Me(3)C(6)H(2)CH(2))NCH(2)CH(2)N(R)Cdbond;](2) (2a: R=CH(2)CH(2)OMe, 2 b R=CH(2)Mes), bearing at least one 2,4,6-trimethylbenzyl (R=CH(2)Mes) group on the nitrogen atom, with [RuCl(2)(arene)](2) (arene=p-cymene, hexamethylbenzene) selectively leads to two types of complexes. The cleavage of the chloride bridges occurs first to yield the expected (carbene) (arene)ruthenium(II) complex 3. Then a further arene displacement reaction takes place to give the chelated eta(6)-mesityl,eta(1)-carbene-ruthenium complexes 4 and 5. An analogous eta(6)-arene,eta(1)-carbene complex with a benzimidazole frame 6 was isolated from an in situ reaction between [RuCl(2)(p-cymene)](2), the corresponding benzimidazolium salt and cesium carbonate. On heating, the RuCl(2)(imidazolinylidene) (p-cymene) complex 8, with p-methoxybenzyl pendent groups attached to the N atoms, leads to intramolecular p-cymene displacement and to the chelated eta(6)-arene,eta(1)-carbene complex 9. On reaction with AgOTf and the propargylic alcohol HCtbond;CCPh(2)OH, compounds 4-6 were transformed into the corresponding ruthenium allenylidene intermediates (4-->10, 5-->11, 6-->12). The in situ generated intermediates 10-12 were found to be active and selective catalysts for ring-closing metathesis (RCM) or cycloisomerisation reactions depending on the nature of the 1,6-dienes. Two complexes [RuCl(2)[eta(1)-CN(CH(2)C(6)H(2)Me(3)-2,4,6)CH(2)CH(2)N- (CH(2)CH(2)OMe)](C(6)Me(6))] 3 with a monodentate carbene ligand and [RuCl(2)[eta(1)-CN[CH(2)(eta(6)-C(6)H(2)Me(3)-2,4,6)]CH(2)CH(2)N-(CH(2)C(6)H(2)Me(3)-2,4,6)]] 5 with a chelating carbene-arene ligand were characterised by X-ray crystallography.     

PHA-L lectin and carbohydrate relationship: conjugation with CdSe/CdS nanoparticles, radiolabeling and in vitro affinities on MCF-7 cells

This research aims to investigate the interaction between phytohemagglutinin-L (PHA-L) and sialic acid, which is abundant on the breast cancer cell (MCF-7) surface and displays monosaccharide characteristics, by experimental and computational methods. Experimentally, CdSe/CdS nanoparticles (QDs) were synthesized; PHA-L was conjugated with QDs and labeled with ¹²⁵I. Radiolabeling yield was found to be 97 ± 1.2 %. Afterwards, in vitro bioaffinities of radiolabeled PHA-L conjugated QDs have been investigated on MCF-7 cells and it has been observed that the cell incorporation increased with time. The results indicated that ¹²⁵I labeled QD-PHA-L conjugates represent significant affinity on MCF-7 cells. In the second step of the study, the crystal structure of carbohydrate interaction surface of PHA-L was extracted from the crystal structure of PHA-L. The interactions between this surface and sialic acid were calculated by computational tools. These calculations revealed specific interactions between PHA-L and sialic acid. Semi-empirical methods, PM3 and AM1, were used in these calculations. Significant outcomes have been obtained from the experimental and computational studies and these results demonstrated that PHA-L may be an effective agent for imagining MCF-7 cells.     

Total Synthesis of the Anti‐inflammatory and Pro‐resolving Lipid Mediator MaR1n−3 DPA Utilizing an sp3–sp3 Negishi Cross‐Coupling Reaction

The first total synthesis of the lipid mediator MaR1_{n?3 DPA} ( 5 ) has been achieved in 12 % overall yield over 11 steps. The stereoselective preparation of 5 was based on a Pd‐catalyzed sp³–sp³ Negishi cross‐coupling reaction and a stereocontrolled Evans–Nagao acetate aldol reaction. LC‐MS/MS results with synthetic material matched the biologically produced 5 . This novel lipid mediator displayed potent pro‐resolving properties stimulating macrophage efferocytosis of apoptotic neutrophils.     

Faithful qubit distribution assisted by one additional qubit against collective noise

We propose a distribution scheme of polarization states of a single photon over a collective-noise channel. By adding one extra photon with a fixed polarization, we can protect the state against collective noise via a parity-check measurement and postselection. While the scheme succeeds only probabilistically, it is simpler and more flexible than the schemes utilizing decoherence-free subspace. An application to the Bennett-Brassard 1984 protocol through a collective-noise channel, which is robust to the Trojan horse attack, is also given.     

Asymmetric solution-phase mixture aldol reaction using oligomeric ethylene glycol tagged chiral oxazolidinones

Sorting tags are oligomeric structures that can be used as protecting groups or chiral auxiliaries enabling solution-phase mixture syntheses of multiple tagged compounds in one pot and allowing for facile and predictable chromatographic separation of products at the end of synthetic sequences. Perfluorinated hydrocarbon and oligomeric ethylene glycol (OEG) derivatives are known classes of sorting tags. Herein we describe the preparation of OEGylated chiral oxazolidinones and their use in asymmetric solution-phase mixture aldol reactions. Through the use of such oxazolidinones based on tyrosine four different individually tagged aldol adducts were obtained as a mixture, chromatographically demixed, detagged, and it was shown that these processes gave the desired aldol products in good yield and enantioselectivity.